CN106965499B - Porous composite film and preparation method thereof - Google Patents
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- CN106965499B CN106965499B CN201710085430.1A CN201710085430A CN106965499B CN 106965499 B CN106965499 B CN 106965499B CN 201710085430 A CN201710085430 A CN 201710085430A CN 106965499 B CN106965499 B CN 106965499B
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- 239000002131 composite material Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229920000642 polymer Polymers 0.000 claims abstract description 28
- 229920006217 cellulose acetate butyrate Polymers 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000005266 casting Methods 0.000 claims abstract description 15
- 238000005303 weighing Methods 0.000 claims abstract description 11
- 238000001125 extrusion Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000010030 laminating Methods 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 7
- -1 polypropylene Polymers 0.000 claims description 18
- 239000004952 Polyamide Substances 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 9
- 239000004743 Polypropylene Substances 0.000 claims description 9
- 229920002647 polyamide Polymers 0.000 claims description 9
- 229920000573 polyethylene Polymers 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 229920006149 polyester-amide block copolymer Polymers 0.000 claims description 6
- 239000012528 membrane Substances 0.000 abstract description 17
- 239000011148 porous material Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003811 acetone extraction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/266—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/202—Conductive
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/204—Di-electric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to the field of composite membranes, in particular to a porous composite membrane and a preparation method thereof, wherein the porous composite membrane comprises a base membrane, an outer layer porous membrane is attached to the outer surface of the base membrane, holes are uniformly distributed on the outer layer porous membrane, the average diameter of the holes is 1-10 mu m, and the preparation method of the porous composite membrane comprises the following steps of 1) weighing outer layer polymers according to the mass ratio: cellulose acetate butyrate is 6.5: 3.5-9: 1, the cellulose acetate butyrate is uniformly mixed to serve as an outer layer film raw material, the outer layer film raw material and a base film polymer are fed into a double-layer casting film machine, and a composite film formed by laminating a base film and an outer layer film is obtained after the extrusion, unidirectional stretching and cooling forming processes of the double-layer casting film machine are carried out; 2) and soaking the composite film in an acetone solution, extracting cellulose acetate butyrate in the outer layer film by using acetone to form an outer layer porous film on the outer layer film, and drying to obtain the porous composite film. The porous composite film has the characteristic of large specific surface area.
Description
Technical Field
The invention relates to the field of composite membranes, in particular to a porous composite membrane and a preparation method thereof.
Background
The composite film is made of a high polymer material compounded by two or more layers of films made of different materials in a gluing or hot pressing mode, and the composite film can be made of multiple layers of films made of different materials, so that the composite film has partial performances of multiple materials and is endowed with more performance combinations. At present, composite films are widely applied to the field of packaging, and researchers gradually apply the composite films to the fields of sensors, supercapacitors, functional fibers and the like because the composite films have the characteristics of strong flexibility, excellent mechanical properties, low production cost and the like.
Disclosure of Invention
In order to solve the above problems, an object of the present invention is to provide a porous composite film having a large specific surface area and a method for preparing the same.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the porous composite film comprises a base film, wherein an outer layer porous film is attached to the outer surface of the base film, holes are uniformly distributed in the outer layer porous film, and the average diameter of the holes is 1-10 micrometers; the base film is one of polypropylene, polyethylene, polyester and polyamide, and the outer porous film is one of polypropylene, polyethylene, polyester and polyamide; the thickness of the base film is 50-100 mu m, and the thickness of the outer porous film is 50-100 mu m.
Preferably, the outer porous film and the base film are made of the same material.
The preparation method of the porous composite film comprises the following steps:
1) weighing outer layer polymers according to mass ratio: cellulose acetate butyrate is 6.5: 3.5-9: 1, the cellulose acetate butyrate is uniformly mixed to serve as an outer layer film raw material, the outer layer film raw material and a base film polymer are fed into a double-layer casting film machine, and a composite film formed by laminating a base film and an outer layer film is obtained after the extrusion, unidirectional stretching and cooling forming processes of the double-layer casting film machine are carried out; the outer layer polymer is one of polypropylene, polyethylene, polyester and polyamide; the base film is one of polypropylene, polyethylene, polyester and polyamide;
2) and soaking the composite film in an acetone solution, extracting cellulose acetate butyrate in the outer layer film by using acetone to form an outer layer porous film on the outer layer film, and drying to obtain the porous composite film.
Preferably, the outer layer polymer is the same material as the base film polymer. The outer layer polymer and the base film polymer are made of the same material, and the porous composite film prepared from the outer layer polymer and the base film polymer has better composite effect of two films and tighter attachment.
Preferably, the thickness of the outer porous film is 50 to 100 μm, and the thickness of the base film is 50 to 100 μm.
Preferably, the average diameter of the holes in the outer porous film is 1-10 μm.
Preferably, the mass ratio of the outer layer film raw material to the base film polymer is 1: 1-2.
The invention has the advantages that:
compared with the traditional composite membrane, the outer-layer membrane of the invention is an outer-layer porous membrane, the specific surface area of the outer layer is enlarged by dozens of times, the porous composite membrane has a micron-order pore structure, and if the porous composite membrane is treated by functional substances, the micron-order pore structure can tightly adsorb the functional substances so as to realize special functions, such as electric conduction, hydrophilicity and hydrophobicity, and can be applied to the fields of special textile fabrics, sensing, super capacitors and the like.
2, after the double-layer casting film machine is compounded, the compounding effect of the outer porous film and the base film is good, and the adhesive is not needed.
3, outer layer polymer: when the ratio of the cellulose acetate butyrate is 6.5: 3.5-9: 1, the cellulose acetate butyrate is uniformly dispersed in the outer-layer polymer, unidirectional drafting is carried out through blending extrusion, and a continuous phase cannot be formed, and after the cellulose acetate butyrate is extracted through acetone, the outer-layer film forms a pore structure, so that the porous composite film is formed. If the mass ratio is more than 9:1, the diameter of the holes in the outer porous film is too large to exceed 10 μm, so that the sensing or adsorption function of the porous composite film is influenced; if the mass ratio is less than 6.5:3.5, the continuous phase cellulose acetate butyrate can be generated through blending, extrusion and unidirectional drafting, and the nanofiber structure is formed after acetone extraction, so that the pore structure cannot be formed.
Drawings
FIG. 1 is a schematic structural diagram of a porous composite membrane according to the present invention;
FIG. 2 is a schematic structural view of the outer porous membrane of FIG. 1;
FIG. 3 is a schematic structural view of the composite film obtained in step 1) in examples 1 to 4;
the components in the figures are numbered as follows: outer porous film 1, base film 2, outer film 3.
Detailed Description
For a better understanding of the present invention, reference will now be made in detail to the present invention, examples of which are illustrated in the accompanying drawings.
Example 1
The preparation method of the porous composite film comprises the following steps:
1) weighing 650g of polypropylene and 350g of cellulose acetate butyrate, uniformly mixing the polypropylene and the cellulose acetate butyrate to be used as outer-layer film raw materials, and then weighing 2000g of polypropylene to be used as a base film polymer; putting the outer layer film raw material and the base film polymer into a double-layer casting film machine, and obtaining a composite film (shown in figure 3) formed by laminating a base film 2 and an outer layer film 3 after the processes of extrusion, unidirectional stretching and cooling forming of the double-layer casting film machine;
2) soaking the composite film in acetone solution, extracting cellulose acetate butyrate in the outer layer film 3 by using acetone to form an outer layer porous film 1 on the outer layer film 3, and drying to obtain the porous composite film (shown in figure 1).
As shown in FIG. 1, the thickness of the outer porous film 1 in the porous composite film is 50 μm, the thickness of the base film 2 is 100 μm, and as shown in FIG. 2, the average diameter of the pores in the outer porous film 1 is 10 μm.
Example 2
1) Weighing 900g of polyethylene and 100g of cellulose acetate butyrate, uniformly mixing the polyethylene and the cellulose acetate butyrate to be used as an outer layer film raw material, and then weighing 1000g of polyethylene to be used as a base film polymer; putting the outer layer film raw material and the base film polymer into a double-layer casting film machine, and obtaining a composite film (shown in figure 3) formed by laminating the outer layer film 3 of the base film 2 after the extrusion, unidirectional stretching and cooling forming processes of the double-layer casting film machine;
2) soaking the composite film in acetone solution, extracting cellulose acetate butyrate in the outer layer film by using acetone to obtain an outer layer porous film 1 formed by the outer layer film 3, and drying to obtain the porous composite film (shown in figure 1).
As shown in FIG. 1, the thickness of the outer porous film 1 in the porous composite film is 100 μm, the thickness of the base film 2 is 50 μm, and as shown in FIG. 2, the average diameter of the pores in the outer porous film 1 is 5 μm.
Example 3
1) Weighing 700g of polyester and 300g of cellulose acetate butyrate, uniformly mixing the polyester and the cellulose acetate butyrate to obtain an outer layer film raw material, and weighing 1500g of polyester to obtain a base film polymer; putting the outer layer film raw material and the base film polymer into a double-layer casting film machine, and obtaining a composite film (shown in figure 3) formed by laminating the outer layer film 3 of the base film 2 after the extrusion, unidirectional stretching and cooling forming processes of the double-layer casting film machine;
2) and (2) soaking the composite film in an acetone solution, extracting cellulose acetate butyrate in the outer layer film by using acetone to form an outer layer porous film on the outer layer film, and drying to obtain the porous composite film (shown in figure 1).
As shown in FIG. 1, the thickness of the outer porous film 1 in the porous composite film is 65 μm, the thickness of the base film 2 is 80 μm, and as shown in FIG. 2, the average diameter of the pores in the outer porous film 1 is 1 μm.
Example 4
1) Weighing 800g of polyamide and 200g of cellulose acetate butyrate, uniformly mixing the polyamide and the cellulose acetate butyrate to serve as an outer layer film raw material, and weighing 1000g of polyamide to serve as a base film polymer; putting the outer layer film raw material and the base film polymer into a double-layer casting film machine, and obtaining a composite film (shown in figure 3) formed by laminating the outer layer film 3 of the base film 2 after the extrusion, unidirectional stretching and cooling forming processes of the double-layer casting film machine;
2) and (2) soaking the composite film in an acetone solution, extracting cellulose acetate butyrate in the outer layer film by using acetone to form an outer layer porous film on the outer layer film, and drying to obtain the porous composite film (shown in figure 1).
As shown in FIG. 1, the thickness of the outer porous film 1 in the porous composite film is 70 μm, the thickness of the base film 2 is 75 μm, and as shown in FIG. 2, the average diameter of the pores in the outer porous film 1 is 6 μm.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (1)
1. A preparation method of a porous composite film is characterized by comprising the following steps: the method comprises the following steps:
1) weighing outer layer polymers according to mass ratio: cellulose acetate butyrate is 6.5: 3.5-9: 1, the cellulose acetate butyrate is uniformly mixed to serve as an outer layer film raw material, the outer layer film raw material and a base film polymer are fed into a double-layer casting film machine, and a composite film formed by laminating a base film and an outer layer film is obtained after the extrusion, unidirectional stretching and cooling forming processes of the double-layer casting film machine are carried out; the base film and the outer layer film are formed synchronously; the outer layer polymer is one of polypropylene, polyethylene, polyester and polyamide; the base film is one of polypropylene, polyethylene, polyester and polyamide;
2) soaking the composite film in an acetone solution, extracting cellulose acetate butyrate in the outer layer film by using acetone to form an outer layer porous film on the outer layer film, and drying to obtain a porous composite film;
the outer layer polymer and the base film polymer are the same material;
the thickness of the outer porous film is 50-100 mu m, and the thickness of the base film is 50-100 mu m;
the average diameter of the holes in the outer porous film is 1-10 mu m;
the mass ratio of the outer layer film raw material to the base film polymer is 1: 1-2.
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CN107366195A (en) * | 2017-09-20 | 2017-11-21 | 武汉菡美洛建筑材料有限公司 | A kind of light soft sound insulation high-adhesiveness wallpaper and its manufacture method |
CN109111664A (en) * | 2018-07-11 | 2019-01-01 | 四川羽玺新材料股份有限公司 | A kind of PVDF-PET/ graphene quantum dot composite membrane and preparation method thereof |
CN111455566B (en) * | 2020-03-10 | 2021-12-24 | 武汉纺织大学 | Composite nanofiber membrane and preparation method thereof |
CN111752013B (en) * | 2020-06-29 | 2022-08-09 | 绍兴迪飞新材料有限公司 | Porous polymer optical thin film device and preparation method thereof |
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CN1159770A (en) * | 1994-07-28 | 1997-09-17 | 米利波尔公司 | Porous composite membrane and making process |
CN105140452A (en) * | 2015-08-12 | 2015-12-09 | 深圳市星源材质科技股份有限公司 | Polyolefin composite microporous membrane with low hot-shrinkage rate and preparation method |
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CN1159770A (en) * | 1994-07-28 | 1997-09-17 | 米利波尔公司 | Porous composite membrane and making process |
CN105140452A (en) * | 2015-08-12 | 2015-12-09 | 深圳市星源材质科技股份有限公司 | Polyolefin composite microporous membrane with low hot-shrinkage rate and preparation method |
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